Structural and spectroscopic study of 5,7-dihydroxy-flavone and its complex with aluminum

The structure, stability and molar absorptivity of the complex formed between AlCl(3) and 5,7-dihydroxy-flavone in methanol were investigated using UV-Vis spectroscopy and the AM1 method. The molar ratio method and Job's method of continuous variation were applied to ascertain the stoichiometric composition of the complex in methanol at constant ionic strength. A 1:2 complex was indicated by both methods. The molar absorptivity and stability constant of the complex were determined using a simple and accurate procedure that requires solutions having the ligand and metal ion in the stoichiometric proportion. The high stability constant demonstrates that the complexation reaction is total. The structure of this complex, obtained by the quantum semi-empirical AM1 method, indicates that two classes of metal-ligand interactions are involved in the formation of the metal complex: (a) two simple covalent bonds between the aluminum atom and the oxygen atoms of o-hydroxyl groups of 5,7-dihydroxy-flavone; (b) two stronger Coulombic interactions between the aluminum atom and the carbonyl oxygen atoms of the ligand.     

Alkoxide-induced reactions of N-substituted saccharins. Synthesis of 1,2-benzothiazocine 1,1-dioxide and 2,3-dihydropyrrolo[1,2-b]-[1,2]benzisothiazole 5,5-dioxide derivatives

The reactions of saccharin derivatives 1 with sodium alkoxides were studied. Under mild conditions, compounds 1a-f gave the corresponding open sulfonamides 5a-f . Under drastic conditions, β-(saccharin-2)propionic acid derivatives 1a,b reacted with sodium ethoxide affording saccharin and β-ethoxypropionic acid derivatives 4a,b . γ-(Saccharin-2)butyric acid derivatives 1c,d and γ-(saccharin-2)-butyrophenone 1f reacted with sodium t-butoxide in dimethyl sulfoxide affording 5-substituted 6-hydroxy-3,4-dihydro-2H-1,2-benzothiazocine 1,1-dioxides 9 . From mother liquors, 1-substituted 2,3-dihydro-pyrrolo[1,2-b][1,2]benzisothiazole 5,5-dioxides 10 were isolated several hours later, though not detected immediately after completing the reaction. When the reactions were carried out in t-butyl alcohol, the yields of 9 diminished and those of 10 increased with product ratio inversion. Different experimental observations on the possible pathway generating 9 and 10 are discussed.     

Dimensional Matching of Polycyclic Aromatics with Rectangular Metallacycles: Insertion Modes Determined by [C?H⋅⋅⋅π] Interactions

A family of Pd^II/Pt^II dinuclear receptors, designed to give a smooth increase in their cavity lengths (from 7.46–13.78 Å), is presented. Their inclusion complexes with a representative set of polycyclic aromatic substrates (naphthalene, carbazol, pyrene, and benzo[a]pyrene), were characterized and studied in aqueous solution and the solid state. By taking into account the dimensions of both receptors and substrates, an excellent complementarity was found between the size of the receptors and their ability to complex a given substrate. Furthermore, this dimensional matching results in specific binding modes depending on the ability of the guest to establish stabilizing [C? H???π] interactions with the host.     

Simultaneous spectrophotometric determination of Zinc(II) and Nickel(II) with 1-(2-pyridylazo)-2-naphthol

A new procedure for the simultaneous spectrophotometric determination of Zn(II) and Ni(II) with 1-(2-pyridylazo)-2-naphthol as chromogenic reagent has been developed. It is based on resolution of the mixed spectrum over the wavelength range 530–590 nm by applying a least-squares fitting program to standard spectra from each component. The spectra are recorded at an apparent pH of 5.0, provided by an acetate buffer in a mixed 6040 v/v 2-ethoxyethanol/water medium. The relative standard deviations for determination of 13.7 g of Ni and 31.0 g of Zn were 1.9 and 1.0%, respectively (8 replications). The method has been applied to the analysis of iron surfaces coated with a Zn-Ni alloy. The results are compared with those obtained by atomic-absorption spectrophotometry.     

Application of micellar electrokinetic chromatography to the quality control of a pharmaceutical preparation containing three bronchodilators

Theophylline(1,3-dimethylxanthine), dyphylline [7-(2,3-dihydroxypropyl)theophylline] and proxyphylline [7-(beta-hydroxypropyl)theophylline] are three bronchodilators administered jointly in a single pharmaceutical preparation used against asthma. A micellar electrokinetic chromatography (MEKC) method for their resolution using a background electrolyte consisting of 20 mM tetraborate at pH 8.5 and 100 mM sodium dodecyl sulfate is proposed. The method was used to determine the three active principles in a pharmaceutical preparation. The small amount of sample required and the expeditiousness of the procedure allow content uniformity to be determined in individual tablets. The values of the validation parameters for the method (viz. selectivity, linearity, accuracy, precision, limit of detection, limit of quantitation and robustness) are reported. A complete factor design (2(3)x2) including pH, the surfactant concentration and the ionic strength of the background electrolyte as factors was used to estimate robustness. Based on the results, the method is robust enough for quantitation purposes.     

Simple and rapid micellar electrokinetic capillary chromatographic method for simultaneous determination of four antiepileptics in human serum

A very rapid and simple MEKC method was developed for the simultaneous determination of four antiepileptic drugs, ethosuximide (Etho), primidone (Pri), phenytoin (Pht) and carbamazepine (Cbz) in human serum. Sample analysis required only 100 microL of human serum which only needed to be centrifuged, decanted and combined with the running buffer [5.3 mM Na(2)HPO(4)/3.2 mM borax buffer (pH 9.5) containing 55 mM SDS and 3.5% (v/v) acetone]. The analysis was performed in only 10 min into fused-silica capillaries (57 cm total length with 50 microm i.d. and 50 cm to the detector) using the MEKC methodology with diode-array detection at 220 nm. The calibration graphs were established for ethoximide, primidone, phenytoin and carbamazepine between 0 and 20 mg/L. Recoveries were between 85 and 87%. The simplicity of the proposed methodology makes it suitable for routine clinical use, especially for epileptic patients on polytherapy.     

Structure of CdS/SiO2 Nanocomposites: Influence of the Precursor and Cd Concentration

The influence of using TMOS or TEOS in the formation of CdS quantum dots in a silica matrix have been studied by X-ray absorption spectroscopy (XAS). The amount of Cd-S bonds have been monitored as a function of the nominal Cd concentration. The relative amount of CdS crystals depends on the precursor. The use of TEOS is not recommended because it gives a poor yield, especially for high Cd concentration. A discussion of the influence of CdS concentration in matrices from TMOS is carried out from structural models created from their pore volume distribution. The mean pore size becomes smaller and the size distribution more uniform when CdS concentration increases but the nanocrystals of low CdS nominal content present a more efficient quantum confinement.     

Derivative spectrophotometric resolution of mixtures of the food colourants Tartrazine, Amaranth and Curcumin in a micellar medium

A study of the absorption spectra of the food colourants Tartrazine (E-102), Amaranth (E-123) and Curcumin (E-100) in various organic solvents and pH media, have been carried out. In addition, the spectral behaviour in aqueous micellar systems of anionic, cationic and non-ionic surfactants, as well as beta-cyclodextrin, was investigated. Analytical methods are proposed for the determination of the three dyes in mixtures without any prior separation step, by the application of the derivative technique to the normal absorption spectra, based on the use of cetyltrimethylammonium bromide (CTAB) in 0.1 M NaOH, over the concentration range 2-50 mug ml(-1). The methods are applied for determining the three dyes in commercial food products.     

Resolution of benzo[a]pyrene in complex mixtures of other polycyclic aromatic hydrocarbons. Comparison of two spectrofluorimetric methods applied to water samples

Two spectrofluorimetric methods, second-derivative constant-energy synchronous luminescence (SDCESL) and constant-wavelength synchronous luminescence (CWSL) in combination with multiple linear regression (MLR), for the quantification of benzo[a]pyrene (BaP) at sub-ng mL-1 levels, in the presence of benzo[b]fluoranthene (BbFt), benzo[k]fluoranthene (BkFt), benzo[ghi]perylene (BghiP) and indeno[1,2,3-cd]pyrene (IP), were developed and compared in detail. SDCESL presents lower limits of detection and quantification than CWSL/MLR and also gives more exact and precise results for levels close to the quantification limit. For BaP, SDCESL achieved quantification limits of 0.019 ng mL-1 in river waters and 0.007 ng mL-1 in drinking waters. This work offers a sensitive, precise, accurate, rapid, simple and economic methodology for monitoring BaP in waters for public consumption, meeting all the requirements of the EC Directive 98/83/CE that fixes the maximum admissible limit for this polycyclic aromatic hydrocarbon in drinking waters at of 0.010 ng mL-1.     

Determination of the rates of formation and hydrolysis of the Schiff bases formed by pyridoxal 5′-phosphate and hydrazinic compounds

The macroscopic rate constants of formation (k₁) and hydrolysis (k₂) for the reactions of pyridoxal 5′-phosphate (PLP) with hydrazine (PLP-HY system), carbidopa (-hydrazino--methyl-β-(3,4-dihydroxyphenyl)propionic acid, PLP-CD system), hydralazine (1-hydrazinophthalazine, PLP-HL system) and isoniazid (4-pyridinecarboxylic acid hydrazide, PLP-ISO system) were fitted to a kinetic scheme that considers the different ionic species present in the medium, their protonation constants, and their individual rates of formation (k₁ⁱ) and hydrolysis (k₂ⁱ). The results obtained for the molecules bearing the hydrazine group are compared with those for the reactions of PLP with n-hexylamine (PLP-NHA system) and poly- -lysine (PLP-LYS system). Some structural effects on the individual rate constants are also examined.